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EP1247843A2 - Composition de revêtements durcissable sous UV pour fibre optique durcissant rapidement et présentant une adhérence améliorée au verre - Google Patents

Composition de revêtements durcissable sous UV pour fibre optique durcissant rapidement et présentant une adhérence améliorée au verre Download PDF

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Publication number
EP1247843A2
EP1247843A2 EP02290635A EP02290635A EP1247843A2 EP 1247843 A2 EP1247843 A2 EP 1247843A2 EP 02290635 A EP02290635 A EP 02290635A EP 02290635 A EP02290635 A EP 02290635A EP 1247843 A2 EP1247843 A2 EP 1247843A2
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EP
European Patent Office
Prior art keywords
composition
coating
polyol
present
oligomer
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Granted
Application number
EP02290635A
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German (de)
English (en)
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EP1247843A3 (fr
EP1247843B1 (fr
Inventor
Igor V. Khudyakov
Michael B. Purvis
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Draka Comteq BV
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Alcatel SA
Nokia Inc
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/02—Optical fibres with cladding with or without a coating
    • G02B6/02395—Glass optical fibre with a protective coating, e.g. two layer polymer coating deposited directly on a silica cladding surface during fibre manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2938—Coating on discrete and individual rods, strands or filaments

Definitions

  • the invention relates to compositions for coating glass surfaces and, more specifically, coating compositions for optical waveguides such as optical fibers, the coating compositions being fast curing and having improved adhesion to glass.
  • Optical fibers made from drawn glass have been used as a reliable transmission medium in telecommunications cables. Glass optical fibers are widely used because they have the ability to carry large amounts of information over long distances.
  • optical fiber waveguides have been coated with plastic compositions of various materials in order to protect the fiber and increase its tensile strength.
  • optical glass fibers are frequently coated with two superposed coatings.
  • the coating which contacts the glass is a relatively soft, primary coating that must satisfactorily adhere to the fiber and be soft enough to resist microbending especially at low service temperatures.
  • the outer, exposed coating is a much harder secondary coating that provides the desired resistance to handling forces yet must be flexible enough to enable the coated fiber to withstand repeated bending without cracking the coating.
  • Coatings are applied to the fiber in-line during fiber drawing.
  • the state of fiber drawing technology has allowed for increased draw speeds to effectuate longer and thinner optical fibers, however, the need for coating compositions that can cure at faster rates coincident with the faster draw speeds has become more urgent. Therefore, it is highly desired for an uncured primary coating to be capable of a high cure speed.
  • the cured primary coating should exhibit good adhesion to glass to prevent delamination of the coating from the optical fiber. Delamination can be caused by excessive moisture. This is particularly devastating to optical fibers as delamination can weaken the optical glass fiber because the delaminated coating can slide against the optical glass fiber causing microscopic scratches. Ultimately, such delamination can result in a loss of optical fiber transmission.
  • adhesion promoting additives have been incorporated into coating compositions.
  • silane adhesion promoters have been used.
  • adhesion promoters can reduce the speed of cure of a coating composition.
  • acrylate oligomers with a polyester or polyether backbone for primary optical fiber coating is known in the field (see U.S. Patent Nos. 5,418,016; 5,650,231; 6,042,943 and 6,048,911). Further, such acrylate oligomers are readily commercially available from a number of manufacturers.
  • U.S. Patent No. 4,849,462 discloses a UV-curable polyurethane polyacrylate containing about 0.5 to 5.0% by weight of a mercapto polyalkoxysilane.
  • U.S. Patent No. 5,812,725 discloses increasing the adhesion of a radiation cured coating for optical glass fibers by the use of an electron beam to adjust the level of adhesion between the primary coating and a surface treated glass optical fiber.
  • This patent generally discloses the use of a reactive diluent which can be a low viscosity acrylate monomer containing at least one functional group capable of polymerization when exposed to actinic radiation.
  • the invention provides for an additional adhesion promoter, but does discuss that such may be unnecessary because of the use of the electron beam to pre-treat the glass fiber.
  • vinyl acrylate specifically.
  • a curable composition can include from about 4.5 to 60 part by weight of a long list of vinyl monomers, including, inter alia , vinyl acrylate, and a vinyl ether, such as the 3:1 adduct of methacrylic acid with tris(4-glycidyloxyphenyl)methane.
  • the curable composition may include a minor amount of a toughness-imparting oligomeric urethane.
  • U.S. Patent No. 5,981,738 discloses the use of ethylenically unsaturated solvents, including vinyl acrylates, capable of free radical addition with maleate or fumarate pendant groups on modified cellulose esters to prepare a UV-curable coating.
  • the amounts of said ethylenically unsaturated solvents used are from between 50 to 90 wt% of the total coating composition.
  • U.S. Patent No. 5,418,016 discloses the use of a N-vinylformamide (NVF) monomer as a reactive diluent, blended with oligomer systems and a photoinitiator to form a radiation curable composition.
  • NVF N-vinylformamide
  • U.S. Patent No. 6,171,698 B1 discloses a radiation curable coating composition having good adhesion.
  • the composition includes a hydrolyzed coupling agent mixture.
  • the present invention provides a new coating composition for optical fibers and optical fibers coated therewith, whereby the coating composition is fast curing and has improved adhesion to glass.
  • the coating composition comprises a radiation curable oligomer and a vinyl acrylate compound that can act as both a reactive diluent and an adhesion promoter, the vinyl acrylate compound having the following formula (I): wherein R is hydrogen or an alkyl group having 1 to 10 carbon atoms.
  • Vinyl acrylate compounds in accordance with the present invention have good miscibility and low viscosity and impart to the cured primary coating a high adhesion to glass, therefore reducing and in some instances even eliminating the need for additional reactive diluent and/or adhesion promoter. With the use of a free radical photoinitiator, the vinyl acrylate compounds increase the speed of cure of the uncured coating in comparison with conventional coating compositions without a vinyl acrylate compound. Cured coating prepared from coating compositions in accordance with the present invention have good adhesion to glass and good stress characteristics.
  • the present invention provides a UV-curable coating formulation for optical fiber.
  • the coating includes a radiation curable oligomer, preferably a urethane acrylate and more preferably a difunctional urethane acrylate with a polyester, polyether, polycarbonate, polybutadience, hydrogenated polybutadience, hydrocarbon or silicone backbone, and a vinyl acrylate compound.
  • a radiation curable oligomer preferably a urethane acrylate and more preferably a difunctional urethane acrylate with a polyester, polyether, polycarbonate, polybutadience, hydrogenated polybutadience, hydrocarbon or silicone backbone, and a vinyl acrylate compound.
  • vinyl acrylate compounds as defined herein are very good reactive diluents, as they are very miscible and have low viscosity (less than 1 cP). Further, during homopolymerization or copolymerization, the vinyl acrylate compound reacts as an acrylate
  • Applicants have also discovered that the addition of a vinyl acrylate compound imparts very good properties to coatings, namely good adhesion to glass. While not wishing to be bound by theory, it is believed that this is due to the presence of non-reacted double bonds in the polymerized vinyl acrylate compound that are capable of forming ⁇ -bonds with active atoms of a glass surface.
  • a vinyl acrylate compound for example, is photosensitive and when irradiated with UV light produces polymer, i.e., polyvinyl acrylate with, as mentioned above, the vinyl ether group staying intact, as can be appreciated from the following: Wherein:
  • the vinyl acrylate compound copolymerizes with other acrylates including the main oligomer, reactive diluents, etc.
  • the vinyl acrylate compound may be present in an amount of about 2 to about 25 wt. %, more preferably, about 5 to about 15 wt.%, and more preferably, about 8 to about 12 wt.%, based upon the total weight of the composition.
  • the particular amount of vinyl acrylate compound will depend upon the efficiency of cure and the desired properties of the cured coating.
  • Suitable vinyl acrylate compounds for use in the present invention such as, for example, vinyl acrylate, are available from Aldrich, Milwaukee, WI.
  • Vinyl acrylate compounds suitable for use in the present invention include compounds within the following formula (I): wherein R is hydrogen or an alkyl group having 1 to 10 carbon atoms.
  • the vinyl acrylate compound is vinyl acrylate (i.e., R is hydrogen) or vinyl methacrylate (i.e., R is a methyl group).
  • the present invention is described herein in the context of a primary coating, as one skilled in the art will recognize, the invention is not limited thereto.
  • the coating composition in accordance with the present invention may be used as a secondary coating composition.
  • Cured primary coatings in accordance with the present invention preferably have a glass transition temperature (T g ) of from about -80°C to about 0°C, more preferably from about -70°C to about -10°C, and most preferably about -60°C to about -40°C, and a low modulus of elasticity of from about 0.2 MPa to about 3 MPa, more preferably from about 0.5 MPa to about 2.0 MPa and most preferably about 1.0-1.5 MPa.
  • T g glass transition temperature
  • Primary coating compositions in accordance with the present invention include a radiation curable oligomer, more preferably, a urethane acrylate oligomer with a molecular weight preferably ranging from about 500 to about 20,000, more preferably from about 5,000 to about 20,000, and most preferably about 5,000 to about 15,000, based upon the specific requirements of the properties of the primary and/or secondary coating in accordance with the present invention (unless otherwise noted, all molecular weights expressed herein are weight average molecular weights).
  • the polydispersity of the acrylate oligomer used in the coating compositions in accordance with the present invention preferably ranges from about 1.1 to about 1.8, more preferably from about 1.1 to about 1.6, and most preferably about 1.2-1.3.
  • Formulation of a primary coating upon addition of a vinyl acrylate compound and other acrylate reactive diluents has a zero-shear viscosity ( ⁇ 0 ) of about 1 x 10 2 to about 1 x 10 4 , more preferably about 5 x 10 2 to about 9 x 10 3 , and most preferably about 5 x 10 3 cP, at 45-50°C, as measured by a rheometer or a viscometer, usually by Brookfield viscometer.
  • the radiation curable oligomer is preferably present in the coating composition of the present invention in an amount of about 40 wt. % to about 95 wt. %, more preferably about 50 wt. % to about 90 wt. %, and most preferably about 60 wt. % to about 80 wt. %, based upon the total weight of the coating composition.
  • the urethane acrylate oligomer of the present invention may be formed by reacting a polyol, for example a diol, with a multifunctional isocyanate, for example, a disocyanate, and then end-capping with a hydroxy-functional acrylate.
  • a polyol for example a diol
  • a multifunctional isocyanate for example, a disocyanate
  • the polyol may be a polyether polyol, a polyester polyol, a polycarbonate polyol, a hydrocarbon polyol, a polybutadiene polyol, copolymers of the previously listed polyols, and mixtures of the foregoing.
  • the polyol may be a polyol with a number average molecular weight of about 200-10,000 g/mol.
  • the polyether polyols may be homopolymers or copolymers of alkylene oxides including C 2 to C 5 alkylene oxides such as, for example, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, and 3-methyltetrahydrofuran; homopolymers or copolymers of the above alkylene oxides obtained by using, as an initiator, C 14 to C 40 polyols, such as 12-hydroxystearyl alcohol and hydrogenated dimerdiol; and adducts of the above alkylene oxides with bisphenol-A or hydrogenated bisphenol-A.
  • These polyether polyols may be used alone or in combination of two or more.
  • Other suitable polyether polyols will be apparent to one skilled in the art.
  • the polyester polyols may be, for example, addition reaction products of a diol component and a lactone, reaction products of the diol component and a polyvalent carboxylic acid, and addition reaction products of three components, including the diol component, a dibasic acid, and the lactone.
  • the diol component may be C 2 to C 40 aliphatic diols with a low molecular weight such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexane glycol, neopentyl glycol, 1,9-nonanediol, 1,10-decanediol, 12-hydroxystearyl alcohol, and hydrogenated dimerdiol; and an alkylene oxide adduct of bisphenol-A.
  • the lactone may be, for example, epsilon-caprolactone, delta-valerolactone, and beta-methyl-delta-valerolactone.
  • the polyvalent carboxylic acid may be, for example, aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid; and aromatic dicarboxylic acids such as hexahydrophthalic acid, tetrahydrophthalic acid, ophthalmic acid, isophthalic acid, and terephthalic acid.
  • Other suitable polyester polyols will be apparent to one skilled in the art.
  • the polycarbonate polyols may be, for example, polycarbonate diols which -are obtainable by a reaction of a short chain dialkylcarbonate and a component selected from aforementioned polyether polyols, polyester polyols and diol components such as 2-methylpropanediol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,5-octanediol, and 1,4-bis-(hydroxymethyl)cyclohexane.
  • the short chain dialkylcarbonate may be C 1 -C 4 alkylcarbonates such as, for example, dimethylcarbonate and diethylcarbonate.
  • Other suitable polycarbonate polyols will be apparent to one skilled in the art.
  • polyols with a relatively low molecular weight may be used.
  • examples of polyols with a relatively low molecular weight include ethylene glycol, propylene glycol, tripropylene glycol, 1,3- or 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, higher fatty acid polyols and higher hydrocarbon polyols such as castor oil, coconut oil, monomyristins (1-monomyristin and 2-monomyristin), monopalmitins (1-monopalmitin and 2-monopalmitin), monostearins (1-monostearin and 2-monostearin), monooleins (1-monoolein and 2-monoolein), 9,10-dioxystearic acid, 12-hydroxyricinoleyl alcohol, 12-hydroxystearyl alcohol, 1,16-hexadecanedi
  • the polybutadiene polyol may be, for example, hydroxyl-terminated, fully or partially hydrogenated 1,2-polybutadiene or 1,2-polybutadiene polyol hydrogenated to an iodine number of from 9 to 21.
  • the multi-functional isocyanate used in the present invention may be, for example, an aromatic polyisocyanate, an aromatic aliphatic polyisocyanate, an alicyclic polyisocyanate, and an aliphatic polyisocyanate.
  • aromatic polyisocyanate examples include diisocyanates such as m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, and 4,4'-diphenyl ether diisocyanate; and polyisocyanates such as triphenylmethane-4,4',4"-triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanatetoluene, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate.
  • diisocyanates such as m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphen
  • aromatic aliphatic polyisocyanate examples include diisocyanates such as 1,3- or 1,4-xylylene diisocyanate or mixtures thereof and 1,3- or 1,4-bis(1-isocyanate-1-methylethyl)benzene or mixtures thereof; and polyisocyanates such as 1,3,5-triisocyanatemethylbenzene.
  • alicyclic polyisocyanate examples include diisocyanates such as 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatemethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 4,4'-methylenebis(cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, and 1,3-or 1,4-bis (isocyanatemethyl)cyclohexane; and polyisocyanates such as 1,3,5-triisocyanatecyclohexane, 1,3,5-trimethylisocyanatecyclohexane, 2-(3-isocyanatepropyl)-2,5-di(isocyanatemethyl)-bicyclo(2.2.1)heptane, 2-
  • aliphatic polyisocyanate examples include diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanatemethylcaproate; and polyisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanateoctane, 1,6,11-triisocyanateundecane, 1,8-diisocyanate-4-isocyanatemethyloctane, 1,3,6-triisocyanatehexane, and 2,5,7-trimethyl-1,8-isocyanate-5-isocyanatemethyloctane
  • derivatives from the above polyisocyanates can be used.
  • the derivatives include a dimer, a trimer, biuret, allophanate, carbodiimide, polymethylenepolyphenyl polyisocyanate (referred to as crude MDI or polymeric MDI), crude TDI, and an adduct of an isocyanate compound and a polyol with a low molecular weight.
  • the hydroxy-functional acrylate may be, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentanediol mono(meth)acrylate, 2-hydroxy-3-phenyloxypropyl (meth)acrylate, 2-hydroxyalkyl(meth)acryloyl phosphate, 4-hydroxycyclohexyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol tri(meth)acrylate.
  • Additional examples include compounds which are obtainable by an addition reaction of a glycidyl group-containing compound and a (meth)acrylic acid, such as alkyl glycidyl ether and glycidyl (meth)acrylate.
  • a glycidyl group-containing compound such as alkyl glycidyl ether and glycidyl (meth)acrylate.
  • the above hydroxyl group-containing (meth)acrylates may be used alone or in combination of two or more.
  • Suitable multifunctional isocyanates are toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), and 4,4' methylene dicyclohexyl diisocyanate (Desmophen W., Bayer Co., Pittsburg, PA USA).
  • Suitable unsaturated monomers containing a hydroxyl group or groups are hydroxyethylacrylate (HEA) and hydroxyethylmethacrylate (HEMA).
  • Suitable polyols are 1,6 hexanediol (Bayer Co. USA), PTG-L 1000 (polyether)(Hodogaya Chemical Co.
  • DuracarbTM 122 Polycarbonate
  • PPG Ind USA
  • polycaprolactones such as the ToneTM polyester series manufactured by Union Carbide Co. USA
  • polybutadiene polyols available from Shell Co. USA as KratonTM.
  • the urethane acrylate oligomer resin useful in accordance with the present invention may have the following general formula (X): R 1 -(I 1 -P-) n -I 2 -R 2 wherein
  • Suitable polyether-based, aliphatic urethane diacrylate compounds for use in the present invention are available from UCB Chemical Corp., of Smynra, GA. They are sold under the name Ebercryl and include Ebecryl 230.
  • Other polyether-based, aliphatic urethane diacrylate compounds suitable for use in the present invention will be apparent to one skilled in the art.
  • other suitable polyether-based, aliphatic urethane diacrylate compounds are disclosed in U.S. Patent Nos. 4,284,731, 4,624,994, 4,607,084, 4,525,258, the disclosures of which are all incorporated herein by reference.
  • Polyester-based, aliphatic urthane acrylate oligomers are available from Sartomer of Exton, PA or from Henkel, Ambler, PA. They are sold under the name CN966XXX, including CN966J75, and Photomer 6010, respectively.
  • Coating compositions in accordance with the present invention will cure without a photoinitiator, albiet after a relatively long period of time. Accordingly, a free radical-type photoinitiator is used in the present invention to initiate polymerization of the urethane acrylate main oligomer and vinyl acrylate compound, and possibly other reactive diluents, if present to tailor the properties of the coating to a particular result.
  • Suitable free radical-type photoinitiators for use in the present invention include, for example, phosphine oxide-type photoinitiators and aromatic ketone-type photoinitiators.
  • the phosphine oxide-type of photoiniators may be a benzoyl diaryl phosphine oxide photoiniator, such as (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (Lucerin TPO available from BASF), or other phosphine oxide-type photoinitiator, such as bis(2,4,6-trimethylbenzoyl) phenyphosphine oxide (Irgacuce 819 available from Ciba Additives of Tarrytown, N.Y.), or bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and mixtures of phosphine oxide-type free radical photoinitiators.
  • a benzoyl diaryl phosphine oxide photoiniator such as (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (Lucerin TPO available from BASF)
  • aromatic ketone-type free radical photoinitiators examples include:
  • the photoinitiator may be mixture of phosphine oxide-type free radical photoinitiator and aromatic ketone-type free radical photoinitiator, such as a mixture of (2,6-dimethoxy benzoyl)-2,4,4 trimethylpentylphosphineoxide and 2-hydroxy-2-methyl-1-phenyl-propane-1-one (Irgacure 1700 available from Ciba Additives, Tarrytown, N.Y., which is a mixture of 25 wt. % of the former and 75 wt % of the latter).
  • phosphine oxide-type free radical photoinitiator such as a mixture of (2,6-dimethoxy benzoyl)-2,4,4 trimethylpentylphosphineoxide and 2-hydroxy-2-methyl-1-phenyl-propane-1-one (Irgacure 1700 available from Ciba Additives, Tarrytown, N.Y., which is a mixture of 25 wt
  • the free radical photoinitiator is (2,6-dimethoxy benzoyl)-2,4,4 trimethylpentylphosphineoxide or a mixture of (2,6-dimethoxy benzoyl)-2,4,4 trimethylpentylphosphineoxide and 2-hydroxy-2-methyl-1-phenylpropane-1-one.
  • Free radical-type photoinitiators suitable for use in the present invention are available from Ciba Additives of Tarrytown, N.Y. They are sold under the names Irgacure® and Darocur®. Other suitable free radical-type photoinitiators will be apparent to one skilled in the art.
  • the free radical type photoinitiator is preferably present in the coating composition of the present invention in an amount of about 0.1 wt. % to about 20 wt. %, more preferably about 0.5 wt. % to about 10 wt. %, and most preferably about 1.0 wt. % to about 5.0 wt. %, based upon the total weight of the coating composition.
  • the coating composition in accordance with the present invention may include one or more reactive diluents in addition to the vinyl acrylate. That is, the use of the vinyl acrylate in a coating composition in accordance with the present invention may be in place of a conventional reactive diluent that might be utilized but, of course, the use of additional reactive diluent is within the scope of the present invention.
  • additional reactive diluent hooks together chains of the urethane acrylate oligomer.
  • the formulator might find that adequate curing of the coating compositions of the present invention is ensured by the presence of additional reactive diluent as it functions as a solvent improving the solubility of the urethane acrylate oligomer in solution.
  • additional reactive diluent also allows the formulator to adjust the viscosity of the solution to improve processability.
  • the additional reactive diluent may, for example, be a lower molecular weight, liquid acrylate-functional compound including one or more of the following diacrylates and monofunctional acrylates:
  • lower molecular weight, liquid monofunctional acrylate compounds suitable for use as an additional reactive diluent in accordance with the present invention are isobornyl acrylate and n-vinyl caprolactam.
  • Other reactive diluents suitable for use in the present invention in combination with the vinyl acrlate will be apparent to one skilled in the art.
  • Reactive diluent in addition to vinyl acrylate may be used in the coating composition in accordance with the present invention in an amount of from about 5 to about 80% by weight, preferably from about 5 to about 60% by weight, and most preferably about 30% by weight, based upon the total weight of the composition.
  • the coating compositions in accordance with the present invention may also include one or more adhesion promoters in addition to the vinyl acrylate which itself acts as an adhesion promoter in accordance with the present invention.
  • Suitable adhesion promoters for purposes of the present invention include acid functional materials and organofunctional silanes.
  • the organofunctional silane may be an amino-functional silane, an acrylamido-functional silane, a mercapto-functional silane, an allyl-functional silane, a vinyl-functional silane, a methylacrylate-functional silane, and an acrylate-functional silane.
  • the organofunctional silane is mercaptoalkyl trialkoxy silane, a methacryloyxlalkyl trialkoxy silane, an aminoalkyl trialkoxyl silane, a vinyl trialkoxyl silane and mixtures thereof.
  • the organofunctional silane is 3-aminopropyl triethoxy silane, 3-methacryloxy-propyltrimethoxy silane, gamma- mercaptopropyl trimethoxy silane, gama-mercaptopropyl (gamma-mercaptopropyl)triethoxy silane, beta-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, gamma-glycidoxypropyl trimethoxy silane, 3-vinylthiopropyl trimethoxy silane, vinyl-tris-(beta-methoxyethoxy) silane, vinyl triacetoxy silane, and mixtures thereof.
  • a particularly preferred adhesion promoter is KBM 803 availiable from Shin-Etsu Silicones of America, Inc, of Torrance, CA.
  • An additional adhesion promoter may be present in the coating composition in accordance with the present invention in an amount of from about 0.1 to about 10% by weight, more preferably from about 0.1 to about 3% by weight, and most preferably less than about 1% by weight, based upon the total weight of the composition.
  • antioxidants include antioxidants, flow control agents, sensitizers, stabilizers, lubricants and wetting agents, as is conventional in the art.
  • the present formulation may include photosensitizers which absorb UV or visible light and transfer energy to the photoinitiators which induces additional decomposition of the photoinitiators with subsequent free radical formation.
  • photosensitizers examples include thioxanthen-9-one, 2-isopropylthioxanthen-9-one and 10-phenylphenoxazine.
  • the photosensitizer, if used, may be present in the coating composition in accordance with the present invention in an amount of from about 0.25 to about 10% by weight, more preferably about 0.25 to about 5% by weight, and most preferably about 1% by weight based upon the total weight of the composition.
  • an optical fiber may be coated with the coating composition in accordance with the present invention by any conventional optical fiber production technique.
  • the conventional techniques usually involve a draw tower in which a preformed glass rod is heated to produce a thin fiber of glass. The fiber is pulled vertically through the draw tower and, along the way, the fiber passes through one or more coating stations at which various coatings are applied and cured in-line to the newly drawn fiber.
  • the coating stations may each contain a die having an exit orifice that is sized to apply the particular coating to the fiber in a desired thickness. Monitoring and measuring devices may be provided near each station to ensure that the coating applied at that station is coated concentrically and to the desired diameter.
  • Optical fiber coating techniques that may be utilized in the present invention are disclosed in U.S. Patent Nos. 4,374,161; 5,858,053; 4,962,992; 5,104,433, the disclosures of which are incorporated herein by reference.
  • Other suitable optical fiber coating techniques that may be utilized in the present invention would be apparent to one skilled in the art.
  • a coating composition was prepared of the following ingredients in the amounts specified in a standard manner by adding all inputs to the diisocyanate at elevated temperature:
  • Films of the foregoing coating composition were made on plain glass plates and allowed to rest for 7 days in a dark area in a room with controlled temperature and humidity (temperature 75 °C, relative humidity RH ⁇ 50%). Adhesion of the films was determined in accordance with the method disclosed in U.S. Patent No. 6,171,698 using an average load of 10-50 mm (N Force), was 0.84 +/- 0.07 N. A rather high peel off force was measured in the experiments, namely 0.84 ⁇ 0.07 N.
  • test samples were prepared by casting a film of the coating having a thickness in the range of 0.02 mm to 0.4 mm, on a glass plate.
  • the cast film was cured using an Iwasaki UV processor.
  • a specimen approximately 25 mm in length and 6.25 mm wide was cut from a defect-free region of the cured film.
  • the film thickness was measured at three or more locations along the length of the sample.
  • the average film thickness was calculated to 0.001 mm. The thickness can not vary by more than 0.01 mm over this length. If the above condition was not met, the sample was discard.
  • the width of the sample was measured at two or more locations and the average value calculated to 150 ⁇ m.
  • the measured geometry of the samples was entered into the Rheometrics OrchestratorTM software.
  • the length filed was set at a value of 22.5 mm and the average values of width and thickness were entered into the appropriate fields.
  • the temperature sweep used included cooling the test samples to -80°C and increasing the temperature at about 3°C per minute until the temperature reached 100°C.
  • the test frequency used was 62.8 rad/s.

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  • Wood Science & Technology (AREA)
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  • Paints Or Removers (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)
EP02290635A 2001-03-30 2002-03-13 Composition de revêtements durcissable sous UV pour fibre optique durcissant rapidement et présentant une adhérence améliorée au verre Expired - Lifetime EP1247843B1 (fr)

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US821154 1997-03-20
US09/821,154 US6470128B1 (en) 2001-03-30 2001-03-30 UV-curable coating composition for optical fiber for a fast cure and with improved adhesion to glass

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EP2103297A1 (fr) 2008-03-20 2009-09-23 Ivoclar Vivadent AG Composition polymérisable contenant des initiateurs comprenant plusieurs atomes de Germanium
US7605190B2 (en) 2006-09-27 2009-10-20 Ivoclar Vivadent Ag Polymerizable compositions with acylgermanium compounds
DE102008047006A1 (de) 2008-09-12 2010-03-25 Heinrich-Heine-Universität Düsseldorf Lichthärtende Zusammensetzungen
WO2017055209A1 (fr) 2015-09-29 2017-04-06 Ivoclar Vivadent Ag Photoarmorceurs à base d'acyl-germanium et leur procédé de fabrication
EP3293215A1 (fr) 2016-09-07 2018-03-14 Ivoclar Vivadent AG Compositions polymérisables avec photoinitiateurs acylzinn
EP3668931A4 (fr) * 2017-08-17 2021-04-07 Khalifa University of Science and Technology Revêtements de nanocontenants à base de carbone mésoporeux pour la protection contre la corrosion de structures métalliques
US11339288B2 (en) 2017-11-10 2022-05-24 Lg Chem, Ltd. Photocurable composition and coating layer including cured product thereof
EP4257592A1 (fr) 2022-04-08 2023-10-11 Evonik Operations GmbH Composés bisacyl digermanium, leur préparation et leur utilisation en tant que photo-initiateur de polymérisation radicalaire

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WO2005081025A1 (fr) * 2004-02-25 2005-09-01 Kansai Paint Co., Ltd. Composition de résine et film sec photoréticulables pour la formation de guide d'onde optique, et guide d'onde optique
US7010206B1 (en) * 2004-09-08 2006-03-07 Corning Incorporated Coated optical fiber and optical fiber coating system including a fast-gelling primary coating
US7811640B2 (en) * 2006-05-02 2010-10-12 Rpo Pty Limited Methods for fabricating polymer optical waveguides on large area panels
FR2904321B1 (fr) * 2006-07-25 2008-09-05 Rhodia Recherches Et Technologies Sas Composition polymerisable et/ou reticulable sous irradiation par voie cationique et/ou radicalaire
CN103009756B (zh) * 2012-12-10 2015-11-18 广东天安新材料股份有限公司 带有表面固化涂层的复合基膜及其制造方法
EP2767520B1 (fr) 2013-02-19 2020-02-19 Teldor Cables & Systems Ltd Revêtement à double couleur de fibres optiques avec des encres durcissables aux UV
US9057817B2 (en) * 2013-04-15 2015-06-16 Corning Incorporated Low diameter optical fiber
CN105705333B (zh) * 2013-11-08 2018-04-13 陶氏环球技术有限责任公司 储存装置
CN107249762B (zh) 2014-11-18 2020-09-22 Ofs菲特尔有限责任公司 低密度可紫外线固化的光纤涂层，用其制造的光纤，和光纤的制造方法
AU2015417227A1 (en) * 2015-12-16 2018-07-19 Politecnico Di Milano Optical fibre with enhanced high temperature resistance
TWI572662B (zh) * 2015-12-30 2017-03-01 奇美實業股份有限公司 熱可塑性樹脂組成物及其所形成的成型品
JP2018077303A (ja) * 2016-11-08 2018-05-17 住友電気工業株式会社 光ファイバ心線
CN107254803B (zh) * 2017-07-14 2019-05-24 上海维凯光电新材料有限公司 用于易碎电子标签纸张的uv涂料及其制备方法
JP7712261B2 (ja) * 2019-07-31 2025-07-23 コベストロ （ネザーランズ） ビー．ブイ． 光ファイバーを被覆するための多官能性長アームオリゴマーを含む放射線硬化性組成物
US11822117B2 (en) * 2019-10-08 2023-11-21 Corning Incorporated Primary coating compositions with improved microbending performance

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Publication number Priority date Publication date Assignee Title
FR2867184A1 (fr) * 2004-03-04 2005-09-09 Cit Alcatel Fibre optique a revetement denudable et procede de denudage d'une telle fibre
WO2005095299A3 (fr) * 2004-03-04 2006-03-16 Cit Alcatel Fibre optique a revetement denudable et procede de denudage d'une telle fibre
US7605190B2 (en) 2006-09-27 2009-10-20 Ivoclar Vivadent Ag Polymerizable compositions with acylgermanium compounds
EP2103297A1 (fr) 2008-03-20 2009-09-23 Ivoclar Vivadent AG Composition polymérisable contenant des initiateurs comprenant plusieurs atomes de Germanium
US8829067B2 (en) 2008-03-20 2014-09-09 Ivoclar Vivadent Ag Polymerizable compositions with initiators containing several Ge atoms
DE102008047006A1 (de) 2008-09-12 2010-03-25 Heinrich-Heine-Universität Düsseldorf Lichthärtende Zusammensetzungen
WO2017055209A1 (fr) 2015-09-29 2017-04-06 Ivoclar Vivadent Ag Photoarmorceurs à base d'acyl-germanium et leur procédé de fabrication
EP3293215A1 (fr) 2016-09-07 2018-03-14 Ivoclar Vivadent AG Compositions polymérisables avec photoinitiateurs acylzinn
WO2018046438A1 (fr) 2016-09-07 2018-03-15 Ivoclar Vivadent Ag Compositions polymérisables à photoamorceurs acylétain
EP3668931A4 (fr) * 2017-08-17 2021-04-07 Khalifa University of Science and Technology Revêtements de nanocontenants à base de carbone mésoporeux pour la protection contre la corrosion de structures métalliques
US11339288B2 (en) 2017-11-10 2022-05-24 Lg Chem, Ltd. Photocurable composition and coating layer including cured product thereof
EP4257592A1 (fr) 2022-04-08 2023-10-11 Evonik Operations GmbH Composés bisacyl digermanium, leur préparation et leur utilisation en tant que photo-initiateur de polymérisation radicalaire

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ATE446326T1 (de) 2009-11-15
US20030021565A1 (en) 2003-01-30
CN1224642C (zh) 2005-10-26
US6470128B1 (en) 2002-10-22
CN1379063A (zh) 2002-11-13
DE60234068D1 (de) 2009-12-03
EP1247843A3 (fr) 2003-12-17
EP1247843B1 (fr) 2009-10-21

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